Step-by-step alkylation of polymeric amines

ABSTRACT

The invention relates to the following: a method for step-by-step alkylation of primary polymeric amines by step-by-step deprotonation with a metallo-organic base and a subsequent reaction with an alkyl halide; a method for modifying tertiary polymeric amines with other functional groups; polymers with secondary/tertiary amino groups and with quaternary ammonium groups; polymers with secondary/tertiary amino groups and other functional groups, especially cation exchanger groupings; membranes consisting of the above polymers, either non-crosslinked or ionically or covalently cross-linked; acid-base-blends/membranes, and a method for producing same, consisting of basic polymers with polymers containing sulphonic acid, phosphonic acid or carboxyl groups; the use of ion exchanger polymers as membranes in membrane processes, e.g., polymer electrolyte membrane fuel cells, direct methanol fuel cells, redox batteries, or electrodialysis; the use of the inventive hydrophilic polymers as membranes in dialysis and reverse osmosis, nanofiltration, diffusion dialysis, gas permeation, pervaporation and perstraction.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of the U.S. National Phase ofInternational Application No. PCT/EP00/03914, filed May 2, 2000, nowpublished as WO 00/66254, which claims priority to German PatentApplication No. DE 199 19 708.3, filed Apr. 30, 1999, the entiredisclosure of each of which is hereby incorporated by express referencehereto.

FIELD OF THE INVENTION

[0002] The present invention relates generally to step-by-stepalkylation of primary polymeric amines by step-by-step deprotonationwith a metallo-organic base and a subsequent reaction with an alkylhalide. The present invention further relates to polymers and membranesmade from processes therefor.

BACKGROUND OF THE INVENTION

[0003] There are a number of processes for introducing primary aminogroups into polymers. Two of these shall be mentioned at this point:

[0004] Reduction of the nitro groups of nitrated polymers with reducingagents suitable for this purpose, for example, with sodium dithionite(Naik, H. A.; Parsons, T. W.: Chemical Modification of PolyaryleneEther/Sulphone Polymers: Preparation and Properties of MaterialsAminated on the Main Chain, Polymer 32, 140 (1991)); and

[0005] Introduction of the azide group in lithiated polymers, forexample, lithiated polysulfone (Guiver, M. D.; Robertson, G. P.:Chemical Modification of Polysulfones: A Facile Method of PreparingAzide Derivatives From Lithiated Polysulfone Intermediates,Macromolecules 28, 294-301 (1995)) and subsequent reduction of the azidegroup with sodium borohydride to give the amino group (Guiver, M. D.;Robertson, G. P.; Foley, S.: Chemical Modification of Polysulfones II:An Efficient Method for Introducing Primary Amine Groups onto theAromatic Chain, Macromolecules 28, 7612-7621 (1995)).

[0006] Tertiary amino groups can be introduced into polymers by reactinglithiated polymers with aromatic ketones, aldehydes or carboxylic esterswhich contain tertiary amino groups (Kerres, J.; Ullrich, A.; H˜ring,Th.:Modifikation von Engineeringpolymeren mit N-basischen Gruppen undmit Ionenaustauschergruppen in der Seitenkette [Modification ofEngineering Polymers with N-basic Groups and with Ion Exchanger Groupsin the Side Chaini, German Patent Application 198 365 14.4 dated Aug.12, 1998)

[0007] From the prior art, no reaction is known with which secondaryamino groups can be introduced into a polymer in a targeted manner, noris a reaction known from the prior art with which it is possible toproduce a polymer with secondary amino groups from a polymer withprimary amino groups, and to produce a polymer with tertiary aminogroups from said polymer with secondary amino groups.

[0008] If primary amines are alkylated by means of known processes,tertiary amine and quaternary ammonium salts are also formed in additionto secondary amine. Mixtures of low molecular weight primary, secondaryand tertiary amines can be separated from one another, for example, bymeans of distillation. If, however, the primary amino groups of apolymer are alkylated by means of customary processes, following thereaction, primary, secondary and tertiary amino groups may be presentsimultaneously on a macromolecule. Thus, using customary alkylatingprocesses, it is not possible to obtain secondary or tertiary polymericamines from primary polymeric amines in a targeted manner. Thistechnical problem is solved by this invention.

SUMMARY OF THE INVENTION

[0009] One aspect of the invention relates to

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The invention relates to:

[0011] (1) a process for the stepwise alkylation of primary polymericamines by stepwise deprotonation with an organometallic base andsubsequent reaction with an alkyl halide;

[0012] (2) a process for the modification of tertiary polymeric aminesprepared by process (1) with further functional groups;

[0013] (3) polymers with secondary and/or tertiary amino groups, andwith quaternary ammonium groups, obtained by the process (1);

[0014] (4) polymers with secondary and/or tertiary amino groups andfurther functional groups, in particular cation exchanger groups,obtained by the process (2);

[0015] (5) membranes of the polymers (1), (2), (3), and/or (4), wherethe membranes may be uncrosslinked or ionically crosslinked orcovalently crosslinked;

[0016] (6) a process for the preparation of acid-base blends/acid-baseblend membranes of the basic polymers (1), (2), (3), and/or (4),optionally containing further functional groups, with polymerscontaining sulfonic acid, phosphonic acid or carboxyl groups;

[0017] (7) acid-base blends/acid-base blend membranes, obtainable by theprocess (6), where the blends/blend membranes may additionally also becovalently crosslinked;

[0018] (8) the use of ion exchanger polymers (3), (4), (5), and/or (7)as membranes in membrane processes, such as in polymer electrolytemembrane fuel cells (PEFC), direct methanol fuel cells (DMFC), in redoxbatteries and in electrodialysis; and

[0019] (9) the use of the hydrophilic polymers (3), (4), (5), and/or (7)as membranes in dialysis and reverse osmosis, nanofiltration, diffusiondialysis, gas permeation, pervaporation, and perstraction.

[0020] As a result of this invention, polymers are accessible whichcontain secondary amino groups and/or tertiary amino groups and/orquaternary ammonium groups which can be obtained stepwise from thepolymer modified with primary amino groups. In addition, using thisinvention, polymers are accessible which, in addition to containingtertiary amino groups which have been obtained by stepwise alkylation ofthe primary and of the secondary amino groups, also contain furtherfunctional groups which, following generation of tertiary amino groups,have been introduced in a further reaction step or in two or morefurther reaction steps. Furthermore, membranes of the abovementionedpolymers and from further polymers which can be admixed are accessiblewith this invention.

[0021] For reasons of clarity, the description of the invention isdivided into 3 parts:

[0022] a Stepwise alkylation of the primary amino groups of polymers tothe secondary and tertiary amino groups and to the quaternary ammoniumsalt

[0023] b Introduction of further functional groups into the polymercontaining the secondary and/or tertiary amino groups

[0024] c Acid-base blends of the basic polymers containing the secondaryand/or tertiary amino groups with polymers which contain sulfonate,phosphonate or carboxylate groups.

[0025] Stepwise Alkylation of the Primary Amino Groups of Polymers tothe Secondary and Tertiary Amino Groups and to the Guaternary AmmonlumSalt

[0026] Surprisingly, it has been found that aminated polysulfone PSU,dissolved in tetrahydrofuran (THF), which can be prepared using (Guiver,M. D.; Robertson, G. P.; Foley, S.: Chemical Modification ofPolysulfones II: An Efficient Method for Introducing Primary AmineGroups onto the Aromatic Chain, Macromolecules 28, 7612-7621 (1995)),can be selectively deprotonated by n-butyllithium at the amino group togive the salt PSU—NH⁻Li⁺. The addition of an equimolar amount of methyliodide to the salt PSU—NH⁻Li⁺ gives the secondary polymeric aminePSU—NH—CH₃. This secondary polymeric amine can, surprisingly, in turn bedeprotonated with n-butyllithium to give the salt PSU—N(CH₃)Li. whichcan be reacted with methyl iodide to give the tertiary PSU aminePSU—N(CH₃)₂. If, during the preparation of secondary polymeric aminefrom the primary polymeric amine, the use of a molar deficit of, forexample, n-butyllithium leads to not all NH₂-groups being deprotonatedto NH⁻Li⁺ (the deprotonation yield of n-butyllithium is virtually 100%),following addition of the methyl iodide, polymers can be obtained which,in addition to the alkylated groups NHCH₃, also contain primary aminogroups NH₂ in the desired NHCH₃:NH₂ ratio. If, during the preparation ofthe tertiary polymeric amine from the secondary polymeric amine, the useof a molar deficit of, for example, n-butyllithium leads to not allNHCH₃ groups being deprotonated to NCH₃ ⁻Li⁺ following addition of themethyl iodide, polymers can be obtained which, in addition to thetertiary group N(CH₃)₂, also contain secondary amino groups NHCH₃ in thedesired N(CH₃)₂:NHCH₃ ratio.

[0027] The tertiary PSU-amine can be reacted further to give thequaternary ammonium salt by means of customary processes: (Goerdeler,J.: Herstellung von quartern˜ren Ammoniumverbindungen [Preparation ofquaternary ammonium compounds], Houben-Weyl, Methoden der organischenChemie [Methods of organic chemistry], Volume XI/2Stickstoffverbindungen II [Nitrogen compounds II], Georg Thieme Verlag,Stuttgart, p. 591 f. (1958)). FIG. 1 shows the stepwise alkylation ofaminated PSU to give the tertiary PSU-amine, and FIG. 2 shows thequaternization of the tertiary PSU-amine.

[0028] Introduction of Further Functional Groups into the PolymerContaining the Secondary and/or Tertiary Amino Groups

[0029] The polymer containing the secondary and/or tertiary amino groupscan now be modified with further functional groups. Thus, for example,PSU containing secondary and/or tertiary amino groups can be modifiedwith further functional groups by means of electrophilic substitutionreactions. FIG. 3 shows the electrophilic sulfonation of PSU containingtertiary amino groups with concentrated sulfuric acid.

[0030] The polymer containing tertiary amino groups can be metalatedwith organometallic reagents, and the metalated polymer containingtertiary amino groups can be reacted with virtually all electrophilicreagents, as described in Guiver, M. D.: Aromatic PolysulfonesContaining Functional Groups by Synthesis and Chemical Modification,Dissertation, Carletown University, Ottawa-Ontario Canada (1987);Guiver, M. D.; Kutowy, O.; Apsimon, J. W.: AromatischePolysulfonderivate und Verfahren zu ihrer Herstellung [Aromaticpolysulfone derivatives and processes for their preparation], DElaid-open 36 36 854 A1 (1987) for only lithiated, nonaminated PSU. FIG.4 shows the lithiation of tertiary PSU-amine with subsequent reaction ofthe lithiated PSU containing tertiary amino groups with SO₂Cl₂to givethe PSU which, in addition to tertiary amino groups, also contains SO₂Clgroups. The PSU-amine sulfochloride can be hydrolyzed in a further stepto the PSU-amine-sulfonic acid.

[0031] The reaction of lithiated PSU which contains no tertiary aminogroups with SO₂Cl₂to give the PSU sulfochloride and further to give thePSU-sulfonic acid is described in a patent application (Kerres, J.;Schnurnberger, W.: Modifizierte Polymere und Polymermembrane [ModifiedPolymers and Polymer Membranes], German patent application 198 09 119.2dated Mar. 4, 1998).

[0032] Polymers according to the invention which, in addition to thetertiary amino group, also have other, preferably acidic, groups(examples: SO₃Y, PO₃Y₂—, COOY groups, Y═H, monovalent metal cation)) mayadditionally also be covalently crosslinked according to the followingprocess: the polymer containing the tertiary amino group and thepreferably acidic groups is dissolved in the salt form (Y═Li, Na, K) ina dipolar-aprotic solvent (for example dimethyl sulfoxide DMSO,sulfolane, N,N-dimethylformamide DMF, N,N-dimethyl acetamide DMAc,N-methylpyrrolidineone NMP). A dihaloalkane X—(CH₂)_(n)—x where X=Br orI and n=3-12 is added to the polymer solution in a concentration of from0.1 mol per mole of tertiary amino group to 0.5 mol per mole of tertiaryamino group. During evaporation of the solvent at elevated temperature,the dihaloalkane reacts with the tertiary amino groups with thesimultaneous formation of quaternary ammonium groups and covalentcrosslinking sites (FIG. 5).

[0033] If the acid-base polymer/acid-base polymer membrane is convertedto the acid form by after-treatment in dilute mineral acid, i.e., the X⁻“microions” are replaced by “macroions” of the acidic groups of thepolymer, then intra- and inter-molecular ionic crosslinking of theacid-base polymer is obtained, in addition to the covalent crosslinkingof the polymer, significantly increasing the mechanical and thermalstability of the polymer.

[0034] The Acid-base Blends of the Basic Polymers Containing theSecondary and/or Tertiary Amino Groups with Polymers which ContainSulfonate Phosphonate or Carboxylate Groups

[0035] The secondary and tertiary polymer amines according to theinvention can then be combined with acidic polymers, which may containSO₃Y, PO₃Y₂ or COOY groups (Y═H, monovalent metal cation or NR₃H⁺ (R═H,alkyl, aryl)) to give acid-base blends and acid-base blend membranes,for example in accordance with Kerres, J., Cui, W.:S˜ure-Base-Polymerblends und ihre Verwendung in Membranprozessen[Acid-base polymer blends and their use in membrane processes], Germanpatent application 198 17 376.8 dated Apr. 18, 1998. In this connection,the resulting acid-base blends and blend membranes can also additionallybe covalently crosslinked by means of the following method: an amineaccording to the invention or any desired polymeric tertiary amine(which may also be a polymer with the pyridine radical) is dissolved ina dipolar-aprotic solvent (for example, dimethyl sulfoxide DMSO,sulfolane, N,N-dimethylformamide DMF, N,N-dimethylacetamide DMAc, orN-methylpyrrolidineone NMP) together with a polymer which can containSO₃Y, PO₃Y₂ or COOY groups (Y═H, monovalent metal cation or NR₃H⁺ (R═H,alkyl, aryl)). A dihaloalkane X—(CH₂)_(n)—X where X=Br or I and n=3-12is added to the polymer solution in a concentration of from 0.1 mol permole of tertiary amino group to 0.5 mol per mole of tertiary aminogroup. During evaporation of the solvent at elevated temperature, thedihaloalkane reacts with the tertiary amino groups with the simultaneousformation of quaternary ammonium groups and covalent crosslinking sites(P₁=polymer radical of the basic polymer containing tertiary basicnitrogen):

P₁—NR₂+X—(CH₂)_(n)—X+R₂N—P₁→P₁—NR₂—(CH₂)_(n)—NR₂—P₁

[0036] This means that the basic component of the acid-baseblend/acid-base blend membrane covalently crosslinks with itself and isionically crosslinked with the acidic component if the acid-baseblend/acid-base blend membrane is converted to the acid form, i.e. theX⁻ “microions” in the above reaction equation are replaced by“macroions” of the acidic component (below: —SO₃ ⁻ macroions) of theacid-base blend:

[0037] The above ionic and also covalent crosslinking of theseblends/blend membranes leads to very good mechanical and thermalstabilities.

[0038] Examples of aryl main chain polymers which can be used accordingto the invention are some important engineering thermoplastics such as:

[0039] poly(ethersulfone) PSU Udel® ([R₁—R₅—R₂—R₆—R₂ 13 R₅]_(n); R₂:x=1, R₄=H),

[0040] poly(ethersulfone) PES VICTREX® ([R₂—R₆—R₂—R₅]_(n); R₂: x=1,R₄=H)

[0041] poly(phenylsulfone) RADEL R® ([(R₂)₂—R₅—R₂—R₆—R₂]_(n); R₂: x=2,R₄=H)

[0042] polyetherethersulfone RADEL A®([R₅—R₂—R₅—R₂—R₆]_(n)—[R₅R₂R₆R₂]_(n); R₂: x=1, R₄=H, n/m=0.18),

[0043] poly(phenylene sulfide) PPS ([R₂—R₈]_(n); R₂: x=1, R₄=H)

[0044] poly(phenylene oxide) PPO ([R₂—R₅]_(n); R₄=CH₃)

[0045] The abovementioned novel secondary and tertiary polymer aminesand the process for the preparation thereof have hitherto not beendescribed in the literature. Neither have any polymers which, inaddition to the secondary and tertiary amino groups according to theinvention, also contain further functional groups, in particular cationexchanger groups, become known. Neither have any acid-base blendmembranes of the secondary and/or tertiary polymer amines according tothe invention and from polymers containing cation exchanger groups(SO₃Y, PO₃Y₂ ⁻ or COOY groups, Y═H, monovalent metal cation or NR₃H⁺(R═H, alkyl, aryl)) become known. Likewise, no simultaneously ionicallyand covalently crosslinked acid-base polymers and acid-base polymerblends have become known from the literature.

[0046] The advantages of the invention are:

[0047] Secondary and/or tertiary polymeric amines can be produced in atargeted manner from primary polymeric amines. The yields of thereaction are good, and in the case of mixed polymeric amines accordingto the invention, the ratio between primary and secondary and betweensecondary and tertiary amino groups can be adjusted in a targetedmanner.

[0048] From the resulting tertiary polymeric amines it is possible, in atargeted manner, to prepare quaternary ammonium salts which areuncrosslinked or crosslinked to the desired degree (anion exchangerpolymers and membranes)

[0049] Further functional groups can be introduced in a targeted mannerinto the secondary and/or tertiary polymeric amines according to theinvention by means of an electrophilic reaction.

[0050] Further functional groups can be introduced in a targeted mannerinto the tertiary polymeric amines according to the invention by meansof metalation and subsequent reaction with a desired electrophilicagent.

[0051] The polymeric amines according to the invention can be reactedwith polymers containing cation exchanger groups as desired to giveacid-base blends.

[0052] The acid-base polymers and acid-base polymer blends according tothe invention can be simultaneously covalently and ionically cros 5linked.

EXAMPLES Examples 1-2

[0053] Reaction of Diaminated PSU (NH₂)₂ with n-butyllithium andSubsequently with Methyl Iodide to Give the Secondary PSU-aminePSU(NHCH₃)₂

[0054] Mixture

[0055] 9.44 g of diaminated PSU (0.02 mol)

[0056] 500 ml of anhydrous THF

[0057] 4 ml of 10 M n-BuLi (0.04 mol)

[0058] 7.6 ml of iodomethane (0.12 mol)

[0059] 37 ml (0.5 mol) of triethylamine

[0060] Experimental Set-up

[0061] 1 L glass reaction flask, mechanical stirrer, condenser, argoninlet, mercury bubbler valve

[0062] Experimental Procedure

[0063] The diaminated PSU is dissolved in THF under argon. It is thencooled to −70° C. The solution is titrated with 2.5 M n-BuLi until thedeep red color of the PSU—NH^(−Li) ⁺ ion arises. The 10 M n-BuLisolution is then injected into the polymer solution. The solution isstirred for 30 minutes. The methyl iodide is then injected into thesolution. The solution decolorizes. The solution is allowed to warm toroom temperature, and the triethylamine is injected in in order todestroy excess methyl iodide. The mixture is heated to 40° C. andstirred for 1 hour. The reaction solution is then precipitated in 21 ofisopropanol. The mixture is stirred for 1 hour and the polymerprecipitate is filtered off. The filter residue is slurried in 1 L ofisopropanol and stirred for 1 day (24 hours). The mixture is thenfiltered again, and the filter residue is stored for 1 day at 70° C. ina drying cabinet in 1 L of water in order to wash amine residues out ofthe polymer. The mixture is filtered again and washed with water untilthe washing solution shows a neutral reaction. The polymer is dried to aconstant weight at 7000 in a vacuum drying cabinet.

[0064] Characterization Results of the Reaction Products from Examples1-2

[0065] Elemental Analysis

[0066] Table 1 gives the results of the elemental analysis of PSU(NH₂)₂,PSU(NHCH₃)₂ and PSU(N(CH₃)₂)₂. Agreement between the calculated andexperimental elemental analysis data is good. TABLE 1 Aminated PSU % C %H % N % S PSU(NH₂)₂ Calculated found 68.6 5.1 5.9 6.8 66.8 5.3 6.4 6.5PSU(NHCH₃)₂ Calculated found 69.6 5.6 5.6 6.4 68.3 5.9 6.1 5.9PSU(N(CH₃)₂)₂ Calculated found 70.4 6.1 5.3 6.1 68.4 5.8 5.9 5.2

[0067] FTIR

[0068] The IR spectra of PSU(NH2)₂, PSU(NHCH₃)₂ and PSU(N(CH₃)₂)₂ areshown in FIG. 6. They have significant differences. The differences areparticularly evident in the wavenumber range 3300 to approximately 3550cm¹, the region of N—H stretching vibrations. Thus, in the case of theprimary PStJ-amine, adjacent symmetrical and asymmetrical N—H stretchingvibrations arise, while in the case of the secondary PSU-amine only oneN—H stretching vibration is of course present, which in the case of thetertiary PSU-amine should have disappeared completely. In the tertiaryPSU-amine spectrum, a N—H stretching vibration is present which ismarkedly attenuated relative to the IR spectrum of the secondaryPSU-amine. This indicates that only a small proportion of secondaryamino groups is still present in the tertiary PSU-amine.

Example 3

[0069] Acid-base Blend Membrane of the Reaction Products from 6.1 and6.2 with Sulfonated PStJ in the SO₃Li Form

[0070] 4.5 g of sulfonated PSU Udel® in the SO₃Li form (IEC=1.6 meq ofSO₃Li/g of polymer) are dissolved in 25 g of N-methylpyrrolidineone. 0.5g of the reaction product from the reactions 6.1/6.2 (2 groups per PSUrepeat unit) is then added to the solution and stirred until dissolved.The [lacuna] is then filtered, degassed and applied in a thin film to aglass plate. The solvent is then evaporated at 12000. The glass plate isthen placed into a bath with demineralized water, and the polymermembrane formed detaches from the glass plate. The membrane is thenafter-treated at 7000 firstly in 10% strength sulfuric acid and then indemineralized water. The membrane is then characterized (see below).

[0071] Characterization Results

[0072] Table 2 shows the characterization results of preparedPSU—NR₂/PSU—SO₃H membranes. TABLE 2 Content of Membrane Type ofPSU-SO₃Li IEC_(measured) Swelling R_(sp)H+ [No.] PSU-NR₂ [% by wt.][nmeq of SO₃H/g] [%] [Ω*cm] M2 Comparison: 90 1.432 22.2 32.4 PSU(NH₂)₂M3 PSU NH(CH₃)₂ 90 1.235 19.5 23.4 M4 PSU (N(CH₃)₂)₂ 90 1.255 23.9 29.5

[0073]FIG. 7 shows the thermogravimetry (TGA) curves of the threemembranes listed in Table 2.

Example 4

[0074] Ionically Crosslinked Acid-base Blend Membrane of the ReactionProduct 6.2 and from Sulfonated Polysulfone in the SO₃H form

[0075] 2.7 g of sulfonated PSU Udel® in the SO₃H form (IEC=1.67 meq ofSO₃H/g of polymer) are dissolved in 15 ml of n-methylpyrrolidineone(NMP). 0.63 ml of triethylamine is then added to the solution in orderto neutralize the sulfonic acid groups of the sulfonated PSU. 0.3 g ofthe reaction product from the reaction 6.2 (PSU(N(CH₃)j₂ is then addedto the solution. The mixture is stirred until the reaction product hasdissolved. A film is then drawn from the polymer solution on a glassplate, and then the solvent is evaporated at temperatures of 70-90-120°C. in a drying cabinet at a pressure below atmospheric pressure of,ultimately, 50 mbar. After the solvent has evaporated, the glass platewith the polymer film is left to cool and then placed into a waterbathso that the polymer film detaches from the glass plate. The membrane isthen after-treated for 24 h at 70-80° C. in 10% strength sulfuric acidand then for 24 h at 60° C. in water. The proton resistance of themembrane is then measured.

[0076] Characterization Result: R_(sp)H⁺=83 Ω*cm

Example 5

[0077] Covalently and Ionically Crosslinked Acid-base Blend Membrane ofthe Reaction Product of Example 2 & Sulfonated Polysulfone in the SO₃Hform

[0078] 2.7 g of sulfonated PSU Udel® in the SO₃H form (IEC=1.67 meq ofSO₃H/g of polymer) are dissolved in 15 ml of N-methylpyrrolidineone(NMP). 0.63 ml of triethylamine is then added to the solution in orderto neutralize the sulfonic acid groups of the sulfonated PSU. 0.3 g ofthe reaction product from the reaction in Example 2 (PSU(N(CH₃)₂)₂) isthen added to the solution. The mixture is stirred until the reactionproduct has dissolved. 37.4 pl of diiodobutane are then injected in. Themixture is stirred for half an hour. A film is then drawn from thepolymer solution on a glass plate, and then the solvent is evaporated attemperatures of 70-90-120° C. in a drying cabinet at a pressure belowatmospheric pressure of, ultimately, 50 mbar. After the solvent hasevaporated, the glass plate with the polymer film is left to cool andthen placed into a waterbath so that the polymer film detaches from theglass plate. The membrane is then after-treated for 24 h at 70-80 C in10% strength sulfuric acid and then for 24 h at 60° C. in water. Theproton resistance of the membrane is then measured.

[0079] Characterization Result: R_(sp)H⁺=83 Ω*cm

What is claimed is:
 1. A process for the stepwise alkylation of primarypolymeric amines in solution or in suspension comprising the steps of:deprotonating a primary amino group on the polymeric amine first with anorganometallic base, after which the carbanion formed therefrom is thenreacted with an alkyl halide to give a secondary amino group; anddeprotonating the secondary amino group again with the organometallicbase, after which the carbanion formed therefrom is then reacted with analkyl halide to give a tertiary amino group.
 2. The process of claim 1,wherein the primary and/or secondary amino group is reacted with lessthan the equimolar amount of organometallic compound, thereby forming apolymer comprising both primary and secondary amino groups, or bothsecondary and tertiary amino groups.
 3. The process of claim 1, whereinthe secondary and/or tertiary amino group further undergoes anelectrophilic substitution reaction to form a non-amino functionalgroup.
 4. The process of claim 1, wherein a polymer containing tertiaryamino groups is formed, wherein deprotonation occurs first by means oforganometallic compounds, after which electrophilic agents areintroduced.
 5. The process of claim 1, wherein the tertiary amino groupis further reacted with an alkyl halide or a mixture of alkyl halides togive a quaternary ammonium salt.
 6. The process of claim 1, wherein theamino group to be alkylated is attached to an aromatic or heteroaromaticgroup of a polymer.
 7. The process of claim 1, wherein the primarypolymeric amine comprises an aryl main chain polymer.
 8. The process ofclaim 7, wherein the aryl main chain polymer comprises the followingbuilding blocks:

wherein R₃ and R₄ each individually comprise a hydrogen, methyl, phenyl,naphthyl, pyridyl, or trifluoromethyl group, or a group having theformula C_(n)H_(2n+1) where n is from 1 to
 20. 9. The process of claim8, wherein the polymer is a polyethersulfone.
 10. The process of claim1, wherein the organometallic base is an organolithium or organosodiumcompound.
 11. The process of claim 10, wherein the organolithiumcompound is n-, sec-, or tert-butyllithium.
 12. The process of claim 1,wherein the solution or suspension comprises ether solvents, aromatics,sulfolane, or mixtures of two of these solvents.
 13. The process ofclaim 12, wherein the ether solvent comprises tetrahydrofuran, glyme,diglyme, triglyme, or dioxane.
 14. The process of claim 13, wherein theether solvent comprises tetrahydrofuran.
 15. The process of claim 12,wherein the aromatic solvent comprises benzene, toluene, or xylene. 16.The process of claim 1, wherein the alkyl halide has the formula:C_(n)H_(2n+1)X, wherein n is from 1 to 12 and X is a chlorine, bromine,or iodine atom.
 17. The process of claim 16, wherein the alkyl halide isan alkyl iodide.
 18. The process of claim 1, wherein the number ofprimary amino groups in the aminated polymer to be alkylated is between0.1 and 4 per polymer repeat unit.
 19. The process of claim 3, whereinthe different type of functional group comprises —C═OR, —SO₃H, or —NO₂.20. The process of claim 4, wherein the electrophilic agent comprisesSO₂, SO₃, SO₂Cl₂, SOCl₂, CO₂, COCl₂, PCl₃, PCl₅, POCl₃, Cl—PO(OR)₂,aromatic ketones, aromatic aldehydes aromatic carboxylic esters, oraromatic carbonyl chlorides.
 21. The process of claim 20, wherein thepolymeric alkylated amines are further substituted to contain one ormore of the following groups: —SO₂Y, —SO₃Y, —SO₂Cl, —SOCl, —COOY,—PO₂H₂, PO₃H₂, or —C═OR, wherein Y comprises a hydrogen atom or amonovalent metal cation.
 22. The process of claim 5, wherein the mixtureof alkyl halides comprise a dihaloalkane which allows covalentcrosslinking off the resulting quaternary ammonium salts.
 23. Theprocess of claim 22, wherein the dihaloalkanes have the formula:X—(CH₂)_(n)—X wherein X is a bromine or an iodine atom, and wherein n isfrom 3 to
 12. 24. A polymer or polymer membrane containing secondaryand/or tertiary amino groups, which is obtained by the process ofclaim
 1. 25. A polymer or polymer membrane containing primary andsecondary amino groups, which is obtained by the process of claim
 1. 26.A polymer or polymer membrane containing secondary and/or tertiary aminogroups, and containing electrophilically induced functional groups,which is obtained by the process of claim
 20. 27. The polymer or polymermembrane of claim 26, wherein the electrophilically introducedfunctional groups comprise SO₃Y— or NO₂—, and wherein Y is a hydrogenatom or a monovalent metal cation.
 28. A polymer or polymer membranecontaining secondary and/or tertiary amino groups, and containingelectrophilically induced functional groups, which is obtained by theprocess of claim
 22. 29. The polymer or polymer membrane of claim 28,wherein the electrophilically induced functional groups are cationexchanger groups.
 30. The polymer or polymer membrane of claim 29,wherein the cation exchanger groups comprise SO₃Y—, COOY—, or PO₃H₂—groups, and wherein Y is a hydrogen atom or a monovalent metal cation.31. The polymer or polymer membrane of claim 24, which is uncrosslinkedor physically crosslinked.
 32. A process for the preparation ofacid-base polymer blends, or membranes containing acid-base polymerblends, of the polymers of claim 24 with an acidic polymer containingsulfonic acid, sulfonic acid salt, phosphonic acid, phosphonic acidsalt, carboxylic acid, or carboxylic acid salt groups, comprising thesteps of: dissolving the basic polymer together with the acidic polymerin a dipolar-aprotic solvent; evaporating the solvent to form anacid-base blend; treating the acid-base blend in dilute mineral acid toform a treated acid-base blend, or membrane containing the treatedacid-base blend.
 33. The process of claim 32, wherein the polymer mainchain of the acidic polymer comprises the following building blocks:


34. The process of claim 32, wherein the polymer main chain of theacidic polymer comprises an aryl ether ketone.
 35. The process of claim34, the acidic polymer comprises a polyether ketone, a polyether etherketone, a polyether ketone ether ketone, a polyether ketone ketone, or acopolymer thereof.
 36. The process of claim 32, wherein thedipolar-aprotic solvent comprises dimethyl sulfoxide, sulfolane,N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidineone.37. A process for covalently crosslinking an acid-base blend, comprisingthe steps of: dissolving the polymer or polymer membrane of claim 24together with an acidic polymer in a dipolar-aprotic solvent to form apolymer solution; adding a dihaloalkane, or a mixture of a dihaloalkaneand a monohaloalkane, to the polymer solution; and evaporating thesolvent at elevated temperature to quaternize the tertiary amino groupsand to form a covalently crosslinked acid-base blend.
 38. The process ofclaim 37, wherein the dihaloalkane, or the mixture of dihaloalkane andmonohaloalkane is present in an amount between 0.05 mol per mole oftertiary amino group and 0.5 mol per mole of tertiary amino group.
 39. Acovalently crosslinked acid-base blend or acid-base blend membrane,which is obtained by the process of claim
 32. 40. A process forcovalently and ionically crosslinking acid-base polymers or acid-basepolymer membranes, comprising the steps of: providing a polymercontaining tertiary amino groups and SO₃Y—, PO₃Y₂—, or COOY— groups,wherein Y is a hydrogen atom or a monovalent metal cation; dissolvingthe polymer in a dipolar-aprotic solvent to form a polymer solution;adding a solvent comprising dihaloalkane, or a mixture of a dihaloalkaneand a monohaloalkane, to the polymer solution; and evaporating thesolvent at elevated temperature to quaternize the tertiary amino groupsand to form a covalently and ionically crosslinked acid-base polymer oracid-base polymer membrane.
 41. The process of claim 40, wherein thedihaloalkane, or the mixture of dihaloalkane and monohaloalkane ispresent in an amount between 0.05 mol per mole of tertiary amino groupand 0.5 mol per mole of tertiary amino group.
 42. The process of claim40, further comprising treating the acid-base blend in dilute mineralacid at a temperature from 60 to 90° C. to form a treated acid-basepolymer, or membrane containing the treated acid-base polymer.
 43. Acovalently and ionically crosslinked acid-base polymer or acid-basepolymer membrane, which is obtained by the process of claim 40.